U.S. patent number 11,271,174 [Application Number 16/313,105] was granted by the patent office on 2022-03-08 for organic molecules for use in organic optoelectronic devices.
This patent grant is currently assigned to CYNORA GmbH. The grantee listed for this patent is CYNORA GMBH. Invention is credited to Larissa Bergmann, Michael Danz, Daniel Zink.
United States Patent |
11,271,174 |
Bergmann , et al. |
March 8, 2022 |
Organic molecules for use in organic optoelectronic devices
Abstract
An organic molecule for use in optoelectronic components is
disclosed having a structure of Formula I ##STR00001## with
X.dbd.CN, D= ##STR00002## wherein # is the point of attachment of
unit D to one of the phenyl rings shown in Formula I; Z is a direct
bond or is selected from the group consisting of CR.sup.3R.sup.4,
C.dbd.CR.sup.3R.sup.4, C.dbd.O, C.dbd.NR.sup.3, NR.sup.3, O,
SiR.sup.3R.sup.4, S, S(O), S(O).sub.2; In each occurrence R.sup.1
and R.sup.2 is the same or different, is H, deuterium, a linear
alkyl group having 1 to 5 C atoms, a linear alkenyl or alkynyl
group having 2 to 8 C atoms, a branched or cyclic alkyl, alkenyl or
alkynyl group having 3 to 10 C atoms, wherein one or more H atoms
can be replaced by deuterium or an aromatic ring system having 5 to
15 aromatic ring atoms, which can in each case be substituted with
one or more radicals R.sup.6; and wherein at least one R.sup.a is
not H, and wherein at least one R.sup.2 is H.
Inventors: |
Bergmann; Larissa (Karlsruhe,
DE), Danz; Michael (Eggenstein-Leopoldshafen,
DE), Zink; Daniel (Bruchsal, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
CYNORA GMBH |
Bruchsal |
N/A |
DE |
|
|
Assignee: |
CYNORA GmbH (Bruchsal,
DE)
|
Family
ID: |
1000006157670 |
Appl.
No.: |
16/313,105 |
Filed: |
June 21, 2017 |
PCT
Filed: |
June 21, 2017 |
PCT No.: |
PCT/EP2017/065227 |
371(c)(1),(2),(4) Date: |
December 24, 2018 |
PCT
Pub. No.: |
WO2018/001822 |
PCT
Pub. Date: |
January 04, 2018 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20190198779 A1 |
Jun 27, 2019 |
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Foreign Application Priority Data
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|
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Jul 1, 2016 [DE] |
|
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102016112082.0 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L
51/0061 (20130101); C07D 209/86 (20130101); H01L
51/0072 (20130101); C09K 11/06 (20130101); C07D
209/88 (20130101); C09K 2211/1007 (20130101); H01L
51/5012 (20130101); H01L 51/4253 (20130101); C09K
2211/1025 (20130101); H01L 51/0003 (20130101); H01L
51/001 (20130101) |
Current International
Class: |
H01L
51/50 (20060101); C09K 11/06 (20060101); C07D
209/86 (20060101); C07D 209/88 (20060101); H01L
51/00 (20060101); H01L 51/42 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
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103168085 |
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Jun 2013 |
|
CN |
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105418486 |
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Mar 2016 |
|
CN |
|
2016178463 |
|
Nov 2016 |
|
WO |
|
PCT/EP2017/065227 |
|
Aug 2017 |
|
WO |
|
Primary Examiner: Clark; Gregory D
Attorney, Agent or Firm: Ryan, Mason & Lewis, LLP
Claims
The invention claimed is:
1. An organic molecule, comprising a structure of Formula I,
##STR00033## with X.dbd.CN and D= ##STR00034## wherein # is the
point of attachment of unit D to a phenyl ring of the structure
according to Formula I; Z is a direct bond or is selected from the
group consisting of CR.sup.3R.sup.4, C.dbd.CR.sup.3R.sup.4,
C.dbd.O, C.dbd.NR.sup.3, NR.sup.3, O, SiR.sup.3R.sup.4, S, S(O) and
S(O).sub.2; in each occurrence R.sup.1 and R.sup.2 are the same or
different and are selected from the group consisting of: H,
deuterium; a linear alkyl group having 1 to 5 C atoms, wherein one
or more H atoms can be replaced by deuterium; a linear alkenyl or
alkynyl group having 2 to 8 C atoms, wherein one or more H atoms
can be replaced by deuterium; a branched or cyclic alkyl, alkenyl
or alkynyl group having 3 to 10 C atoms, wherein one or more H
atoms can be replaced by deuterium; and an aromatic ring system
having 5 to 15 aromatic ring atoms, which can in each case be
substituted with one or more radicals R.sub.6; in each occurrence
R.sup.a, R.sup.3 and R.sup.4 is the same or different and is
selected from the group consisting of: H, deuterium,
N(R.sup.5).sub.2, OH, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2,
OSO.sub.2R.sup.5, CF.sub.3, CN, F, Br, I; a linear alkyl, alkoxy or
thioalkoxy group having 1 to 40 C atoms, which can in each case be
substituted with one or more radicals R.sup.5, wherein one or more
non-adjacent CH.sub.2 groups can be replaced by
R.sup.5C.dbd.CR.sup.5, C.ident.C, Si(R.sup.5).sub.2,
Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or
CONR.sup.5 and wherein one or more H atoms can be replaced by
deuterium, CN, CF.sub.3 or NO.sub.2; a linear alkenyl or alkynyl
group having 2 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; a
branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy
group having 3 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which can in each case be substituted with one or more
radicals R.sup.5; an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which can be substituted with one or more
radicals R.sup.5; and a diarylamino group, diheteroarylamino group
or arylheteroarylamino group having 10 to 40 aromatic ring atoms,
which can be substituted with one or more radicals R.sup.5; in each
occurrence R.sup.5 is the same or different and is selected from
the group consisting of: H, deuterium, N(R.sup.6).sub.2, OH,
Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, CF.sub.3,
CN, F, Br, I; a linear alkyl, alkoxy or thioalkoxy group having 1
to 40 C atoms, which can in each case be substituted with one or
more radicals R.sup.6, wherein one or more non-adjacent CH.sub.2
groups can be replaced by R.sup.6C.dbd.CR.sup.6, C.ident.C,
Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, C.dbd.NR.sup.6, P(.dbd.O)(R.sup.6), SO,
SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; a
linear alkenyl or alkynyl group having 2 to 40 C atoms, which can
in each case be substituted with one or more radicals R.sup.6,
wherein one or more non-adjacent CH.sub.2 groups can be replaced by
R.sup.6C.dbd.CR.sup.6, C.ident.C, Si(R.sup.6).sub.2,
Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.6, P(.dbd.O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or
CONR.sup.6 and wherein one or more H atoms can be replaced by
deuterium, CN, CF.sub.3 or NO.sub.2; a branched or cyclic alkyl,
alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C
atoms, which can in each case be substituted with one or more
radicals R.sup.6, wherein one or more non-adjacent CH.sub.2 groups
can be replaced by R.sup.6C.dbd.CR.sup.6, C.ident.C,
Si(R.sup.6).sub.2, Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, C.dbd.NR.sup.6, P(.dbd.O)(R.sup.6), SO,
SO.sub.2, NR.sup.6, O, S or CONR.sup.6 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which can in each case be substituted with one or more
radicals R.sup.6; an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which can be substituted with one or more
radicals R.sup.6; and a diarylamino group, diheteroarylamino group
or arylheteroarylamino group having 10 to 40 aromatic ring atoms,
which can be substituted with one or more radicals R.sup.6; in each
occurrence R.sup.6 is the same or different and is selected from
the group consisting of: H, deuterium, OH, CF.sub.3, CN, F, Br, I;
a linear alkyl, alkoxy or thioalkoxy group having 1 to 5 C atoms,
wherein one or more H atoms can be replaced by deuterium, CN,
CF.sub.3 or NO.sub.2; a linear alkenyl or alkynyl group having 2 to
5 C atoms, wherein one or more H atoms can be replaced by
deuterium, CN, CF.sub.3 or NO.sub.2; a branched or cyclic alkyl,
alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 5 C atoms,
wherein one or more H atoms can be replaced by deuterium, CN,
CF.sub.3 or NO.sub.2; an aromatic or heteroaromatic ring system
having 5 to 60 aromatic ring atoms; an aryloxy or heteroaryloxy
group having 5 to 60 aromatic ring atoms; and a diarylamino group,
diheteroarylamino group or arylheteroarylamino group having 10 to
40 aromatic ring atoms; wherein each of the radicals R.sup.a,
R.sup.3, R.sup.4 or R.sup.5 can also form a mono- or polycyclic,
aliphatic, aromatic and/or benzoannelated ring system with one or
more further radicals R.sup.a, R.sup.3, R.sup.4 or R.sup.5; and
wherein at least one R.sup.a is not H, and wherein at least one
R.sup.2 is H.
2. The organic molecule according to claim 1, wherein R.sup.1 is H
or methyl and R.sup.2 is H.
3. The organic molecule according to claim 1, wherein D comprises a
structure of Formula IIa: ##STR00035## wherein # and R.sup.a have
the aforestated meanings.
4. The organic molecule according to claim 1, wherein D comprises a
structure of Formula IIb: ##STR00036## wherein in each occurrence
R.sup.b is the same or different and is selected from the group
consisting of: N(R.sup.5).sub.2, OH, Si(R.sup.5).sub.3,
B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, CF.sub.3, CN, F, Br, I; a
linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms,
which can in each case be substituted with one or more radicals
R.sup.5, wherein one or more non-adjacent CH.sub.2 groups can be
replaced by R.sup.5C.dbd.CR.sup.5, C.ident.C, Si(R.sup.5).sub.2,
Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or
CONR.sup.5 and wherein one or more H atoms can be replaced by
deuterium, CN, CF.sub.3 or NO.sub.2; a linear alkenyl or alkynyl
group having 2 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; a
branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy
group having 3 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which can in each case be substituted with one or more
radicals R.sup.5; an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which can be substituted with one or more
radicals R.sup.5; and a diarylamino group, diheteroarylamino group
or arylheteroarylamino group having 10 to 40 aromatic ring atoms,
which can be substituted with one or more radicals R.sup.5; and #
and R.sup.5 have the aforestated meanings.
5. The organic molecule according to claim 1, wherein D comprises a
structure of Formula IIc: ##STR00037## wherein in each occurrence
R.sup.b is the same or different and is selected from the group
consisting of: N(R.sup.5).sub.2, OH, Si(R.sup.5).sub.3,
B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, CF.sub.3, CN, F, Br, I; a
linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms,
which can in each case be substituted with one or more radicals
R.sup.5, wherein one or more non-adjacent CH.sub.2 groups can be
replaced by R.sup.5C.dbd.CR.sup.5, C.ident.C, Si(R.sup.5).sub.2,
Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO, SO.sub.2, NR.sup.5, O, S or
CONR.sup.5 and wherein one or more H atoms can be replaced by
deuterium, CN, CF.sub.3 or NO.sub.2; a linear alkenyl or alkynyl
group having 2 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; a
branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy
group having 3 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C=CR.sup.5, C.ident.C,
Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be replaced by deuterium, CN, CF.sub.3 or NO.sub.2; an
aromatic or heteroaromatic ring system having 5 to 60 aromatic ring
atoms, which can in each case be substituted with one or more
radicals R.sup.5; an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which can be substituted with one or more
radicals R.sup.5; and a diarylamino group, diheteroarylamino group
or arylheteroarylamino group having 10 to 40 aromatic ring atoms,
which can be substituted with one or more radicals; and # and
R.sup.5 have the aforestated meanings.
6. The organic molecule according to claim 4, wherein in each
occurrence R.sup.b is the same or different and is selected from
the group consisting of: Me, .sup.iPr, .sup.tBu, CN, CF.sub.3; Ph,
which can in each case be substituted with one or more radicals
selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
pyridinyl, which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
pyrimidinyl which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
carbazolyl which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
and N(Ph).sub.2.
7. A method for producing an organic molecule according to claim 1,
wherein a in 3 position R.sup.1-substituted and in 4 and 6 position
R.sup.2-substituted 2-bromo-5-fluorobenzonitrile is used as the
educt.
8. An optoelectronic device comprising an organic molecule
according to claim 1.
9. The optoelectronic device according to claim 8, wherein the
optoelectronic device is an organic light-emitting diode, a
light-emitting electrochemical cell, an organic light-emitting
sensor, an organic diode, an organic solar cell, an organic
transistor, an organic field-effect transistor, an organic laser or
a down-conversion element.
10. A composition comprising: (a) at least one organic molecule
according to claim 1 as an emitter and/or a host; (b) one or more
emitter and/or host materials different from the at least one
organic molecule according to claim 1; and (c) optionally one or
more dyes and/or one or more solvents.
11. An optoelectronic device comprising the composition according
to claim 10.
12. The optoelectronic device according to claim 11, comprising: a
substrate; an anode; and a cathode, wherein the anode or the
cathode is disposed on the substrate; and at least one
light-emitting layer disposed between the anode and the cathode and
which comprises the composition according to claim 10.
13. The optoelectronic device according to claim 8, wherein the
organic molecule is one of a luminescent emitter and a host
material in an optoelectronic component.
14. The optoelectronic device according to claim 13, wherein a
proportion of the organic molecule in the luminescent emitter or
the host material is in the range of 1% to 80%.
15. An optoelectronic device comprising an organic molecule
according to claim 2.
16. The optoelectronic device according to claim 15, wherein the
organic molecule is one of a luminescent emitter and a host
material in an optoelectronic component.
17. The optoelectronic device according to claim 8, comprising: a
substrate; an anode; a cathode, wherein the anode or the cathode is
disposed on the substrate; and at least one light-emitting layer
disposed between the anode and the cathode and which comprises the
organic molecule.
18. The organic molecule according to claim 1, wherein Z is a
direct bond.
19. The organic molecule according to claim 5, wherein in each
occurrence R.sup.b is the same or different and is selected from
the group consisting of: Me, .sup.iPr, .sup.tBu, CN, CF.sub.3; Ph,
which can in each case be substituted with one or more radicals
selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
pyridinyl, which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
pyrimidinyl which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
carbazolyl which can in each case be substituted with one or more
radicals selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3, or Ph;
and N(Ph).sub.2.
20. A process for producing an optoelectronic component, comprising
processing of the organic molecule according to claim 1 by a vacuum
vaporization process or from a solution.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. .sctn. 371 to
International Application No. PCT/EP2017/065227, filed Jun. 21,
2017 which claims the benefit of DE 10 2016 112 082.0 filed Jul. 1,
2016, and entitled "ORGANIC MOLECULES, IN PARTICULAR FOR USE IN
OPTOELECTRONIC DEVICES", the disclosures of which are incorporated
by reference herein in their entireties.
FIELD OF INVENTION
The invention relates to purely organic molecules and the use
thereof in organic light-emitting diodes (OLEDs) and in other
organic optoelectronic devices.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the present invention will be described
below in more detail, with reference to the accompanying drawings,
of which: FIG. 1 is an Emission spectrum of Example 1 in 10% PMMA.
FIG. 2 is an Emission spectrum of Example 2 in 10% PMMA. FIG. 3 is
an Emission spectrum of Example 3 in 10% PMMA. FIG. 4 is an
Emission spectrum of Example 5 in 10% PMMA.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE INVENTION
Exemplary embodiments of the invention will now be discussed in
further detail. This invention may, however, be embodied in many
different forms and should not be construed as limited to the
embodiments set forth herein.
The underlying task of the present invention was to provide
molecules which are suitable for use in optoelectronic devices.
The invention provides a new class of organic molecules, which are
suitable for use in organic optoelectronic devices.
The organic molecules according to the invention are purely organic
molecules; i.e. they do not have any metal ions, and thus differ
from the metal complex compounds known for use in organic
optoelectronic devices.
The organic molecules according to the invention are characterized
by emissions in the blue, sky blue, or green spectral range. The
photoluminescence quantum yields of the organic molecules according
to the invention are in particular 20% and more. The molecules
according to the invention in particular exhibit thermally
activated delayed fluorescence (TADF). The use of the molecules
according to the invention in an optoelectronic device, for example
an organic light-emitting diode (OLED), results in higher
efficiencies of the device. Such OLEDs have a higher stability than
OLEDs having known emitter materials and comparable color.
The blue spectral range here is understood to be the visible range
from 430 nm to 470 nm.
The sky blue spectral range here is understood to be the range
between 470 nm and 499 nm.
The green spectral range here is understood to be the range between
500 nm and 599 nm.
The emission maximum is in the respective range.
The organic molecules have a structure of Formula I or consist of a
structure according to Formula I:
##STR00003## with X.dbd.CN, D=
##STR00004## # is the point of attachment of unit D to one of the
phenyl rings shown in Formula I. Z is a direct bond or is selected
from the group consisting of CR.sup.3R.sup.4,
C.dbd.CR.sup.3R.sup.4, C.dbd.O, C.dbd.NR.sup.3, NR.sup.3, O,
SiR.sup.3R.sup.4, S, S(O), S(O).sub.2. In each occurrence R.sup.1
and R.sup.2 is the same or different, is H, deuterium, a linear
alkyl group having 1 to 5 C atoms, a linear alkenyl or alkynyl
group having 2 to 8 C atoms, a branched or cyclic alkyl, alkenyl or
alkynyl group having 3 to 10 C atoms, wherein one or more H atoms
can be replaced by deuterium or an aromatic ring system having 5 to
15 aromatic ring atoms, which can in each case be substituted with
one or more radicals R.sup.6. In each occurrence R.sup.a, R.sup.3
and R.sup.4 is the same or different, is H, deuterium,
N(R.sup.5).sub.2, OH, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2,
OSO.sub.2R.sup.5, CF.sub.3, CN, F, Br, I, a linear alkyl, alkoxy or
thioalkoxy group having 1 to 40 C atoms or a linear alkenyl or
alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl,
alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C
atoms, which can in each case be substituted with one or more
radicals R.sup.5, wherein one or more non-adjacent CH.sub.2 groups
can be replaced by R.sup.5C.dbd.CR.sup.5, C.ident.C,
Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2, C.dbd.O,
C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be substituted with deuterium, CN, CF.sub.3 or NO.sub.2;
or an aromatic or heteroaromatic ring system having 5 to 60
aromatic ring atoms, which can in each case be substituted with one
or more radicals R.sup.5, or an aryloxy or heteroaryloxy group
having 5 to 60 aromatic ring atoms, which can be can be substituted
with one or more radicals R.sup.5, or a diarylamino group,
diheteroarylamino group or arylheteroarylamino group having 10 to
40 aromatic ring atoms, which can be substituted with one or more
radicals R.sup.5. In each occurrence R.sup.5 is the same or
different, is H, deuterium, N(R.sup.6).sub.2, OH,
Si(R.sup.6).sub.3, B(OR.sup.6).sub.2, OSO.sub.2R.sup.6, CF.sub.3,
CN, F, Br, I, a linear alkyl, alkoxy or thioalkoxy group having 1
to 40 C atoms or a linear alkenyl or alkynyl group having 2 to 40 C
atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or
thioalkoxy group having 3 to 40 C atoms, which can in each case be
substituted with one or more radicals R.sup.6, wherein one or more
non-adjacent CH.sub.2 groups can be replaced by
R.sup.6C.dbd.CR.sup.6, C.ident.C, Si(R.sup.6).sub.2,
Ge(R.sup.6).sub.2, Sn(R.sup.6).sub.2, C.dbd.O, C.dbd.S, C.dbd.Se,
C.dbd.NR.sup.6, P(.dbd.O)(R.sup.6), SO, SO.sub.2, NR.sup.6, O, S or
CONR.sup.6 and wherein one or more H atoms can be substituted with
deuterium, CN, CF.sub.3 or NO.sub.2; or an aromatic or
heteroaromatic ring system having 5 to 60 aromatic ring atoms,
which can in each case be substituted with one or more radicals
R.sup.6, or an aryloxy or heteroaryloxy group having 5 to 60
aromatic ring atoms, which can be substituted with one or more
radicals R.sup.6, or a diarylamino group, diheteroarylamino group
or arylheteroarylamino group having 10 to 40 aromatic ring atoms,
which can be substituted with one or more radicals R.sup.6. In each
occurrence R.sup.6 is the same or different, is H, deuterium, OH,
CF.sub.3, CN, F, Br, I, a linear alkyl, alkoxy or thioalkoxy group
having 1 to 5 C atoms or a linear alkenyl or alkynyl group having 2
to 5 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl,
alkoxy or thioalkoxy group having 3 to 5 C atoms, wherein one or
more H atoms can be replaced by deuterium, CN, CF.sub.3 or
NO.sub.2; or an aromatic or heteroaromatic ring system having 5 to
60 aromatic ring atoms or an aryloxy or heteroaryloxy group having
5 to 60 aromatic ring atoms or a diarylamino group,
diheteroarylamino group or arylheteroarylamino group having 10 to
40 aromatic ring atoms. Each of the radicals R.sup.a, R.sup.3,
R.sup.4 or R.sup.5 can also form a mono- or polycyclic, aliphatic,
aromatic and/or benzoannelated ring system with one or more further
radicals R.sup.a, R.sup.3, R.sup.4 or R.sup.5. According to the
invention, at least one R.sup.a is not H and at least one R.sup.2
is H.
In another embodiment, R.sup.1 is H or methyl and R.sup.2 is H.
In one embodiment of the organic molecules, the two Groups D are
identical; in another embodiment, the two Groups D are
different.
In another embodiment of the organic molecules, one Group D or both
Groups D has or have a structure of Formula IIa or consist(s) of a
structure of Formula IIa:
##STR00005## wherein the abovementioned definitions apply for # and
R.sup.a.
In another embodiment of the organic molecules according to the
invention, one Group D has or both Groups D have a structure of
Formula IIb, Formula IIb-2 or Formula IIb-3 or consist(s)
thereof:
##STR00006## wherein In each occurrence R.sup.b is the same or
different, is N(R.sup.5).sub.2, OH, Si(R.sup.5).sub.3,
B(OR.sup.5).sub.2, OSO.sub.2R.sup.5, CF.sub.3, CN, F, Br, I, a
linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or
a linear alkenyl or alkynyl group having 2 to 40 C atoms or a
branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy
group having 3 to 40 C atoms, which can in each case be substituted
with one or more radicals R.sup.5, wherein one or more non-adjacent
CH.sub.2 groups can be replaced by R.sup.5C.dbd.CR.sup.5,
C.ident.C, Si(R.sup.5).sub.2, Ge(R.sup.5).sub.2, Sn(R.sup.5).sub.2,
C.dbd.O, C.dbd.S, C.dbd.Se, C.dbd.NR.sup.5, P(.dbd.O)(R.sup.5), SO,
SO.sub.2, NR.sup.5, O, S or CONR.sup.5 and wherein one or more H
atoms can be substituted with deuterium, CN, CF.sub.3 or NO.sub.2;
or an aromatic or heteroaromatic ring system having 5 to 60
aromatic ring atoms, which can in each case be substituted with one
or more radicals R.sup.5, or an aryloxy or heteroaryloxy group
having 5 to 60 aromatic ring atoms, which can be substituted with
one or more radicals R.sup.5, or a diarylamino group,
diheteroarylamino group or arylheteroarylamino group having 10 to
40 aromatic ring atoms, which can be substituted with one or more
radicals R.sup.5. Otherwise, the above-mentioned definitions
apply.
In another embodiment of the organic molecules according to the
invention, one Group D has or both Groups D have a structure of
Formula IIc, Formula IIc-2 or Formula IIc-3 or consist(s)
thereof:
##STR00007## wherein the abovementioned definitions apply.
In a further embodiment of the organic molecules according to the
invention, in each occurrence R.sup.b is independently selected
from the group consisting of Me, .sup.iPr, .sup.tBu, CN, CF.sub.3,
Ph, which can in each case be substituted with one or more radicals
selected from Me, .sup.iPr, .sup.tBu, CN, CF.sub.3 or Ph,
pyridinyl, pyrimidinyl, carbazolyl, which can in each case be
substituted with one or more radicals selected from Me, .sup.iPr,
.sup.tBu, CN, CF.sub.3, or Ph, and N(Ph).sub.2.
Embodiments of Group D are shown in the following as examples:
##STR00008## ##STR00009## ##STR00010## ##STR00011## wherein the
abovementioned definitions apply for #, Z, R.sup.a and R.sup.6. In
one embodiment, in each occurrence, the radical R.sup.5 is the same
or different and is selected from the group consisting of H,
methyl, ethyl, phenyl and mesityl. In one embodiment, in each
occurrence, the radical R.sup.a is the same or different and is
selected from the group consisting of H, methyl (Me), i-propyl
(CH(CH.sub.3).sub.2) (.sup.iPr), t-butyl (.sup.tBu), phenyl (Ph),
CN, CF.sub.3 and diphenylamine (NPh.sub.2).
In the context of this invention, an aryl group contains 6 to 60
aromatic ring atoms; a heteroaryl group contains 5 to 60 aromatic
ring atoms, at least one of which represents a heteroatom. The
heteroatoms are, in particular, N, O and/or S. In the event that
other definitions, which differ from the stated definitions, for
example with respect to the number of aromatic ring atoms or the
contained heteroatoms, are specified in the description of specific
embodiments of the invention, then these definitions apply.
An aryl group or heteroaryl group is understood to be a simple
aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for
example pyridine, pyrimidine or thiophene, or a heteroaromatic
polycyclic compound, for example phenanthrene, quinoline or
carbazole. In the context of the present application, a condensed
(annelated) aromatic or heteroaromatic polycyclic compound consists
of two or more simple aromatic or heteroaromatic rings which are
condensed with one another.
An aryl or heteroaryl group, which can in each case be substituted
with the abovementioned radicals and which can be linked to the
aromatic or heteroaromatic group via any desired positions, are in
particular understood to be groups which are derived from benzene,
naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene,
chrysene, perylene, fluoranthene, benzanthracene,
benzophenanthrene, tetracene, pentacene, benzopyrene, furan,
benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene,
isobenzothiophene, dibenzothiophene; pyrrole, indole, isoindole,
carbazole, pyridine, quinoline, isoquinoline, acridine,
phenanthridine, benzo-5,6-quinoline, isoquinoline,
benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine,
phenoxazine, pyrazole, indazole, imidazole, benzimidazole,
naphthimidazole, phenanthrimidazole, pyridimidazole,
pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,
napthoxazole, anthroxazole, phenanthroxazole, isoxazole,
1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,
benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline,
pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline,
phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,
1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole,
1,2,3,4-tetrazine, purine, pteridine, indolizine and
benzothiadiazole or combinations of said groups.
A cyclic alkyl, alkoxy or thioalkoxy group is understood here to be
a monocyclic, a bicyclic or a polycyclic group.
Within the scope of the present invention, a C.sub.1 to C.sub.40
alkyl group, in which individual H atoms or CH.sub.2 groups can
also be substituted by the groups mentioned above, are understood
to be, for example, the radicals methyl, ethyl, n-propyl, i-propyl,
cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl,
2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neopentyl,
cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl,
cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl,
2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl,
n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl,
2-bicyclo[2,2,2]-octyl, 2-(2,6-dimethyl)octyl,
3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluorethyl,
2,2,2-trifluorethyl, 1,1-dimethyl-n-hex-1-yl-,
1,1-dimethyl-n-hept-1-yl-, 1,1-dimethyl-n-oct-1-yl-,
1,1-dimethyl-n-dec-1-yl-, 1,1-dimethyl-n-dodec-1-yl-,
1,1-dimethyl-n-tetradec-1-yl-, 1,1-dimethyl-n-hexadec-1-yl-,
1,1-dimethyl-n-octadec-1-yl-, 1,1-diethyl-n-hex-1-yl-,
1,1-diethyl-n-hept-1-yl-, 1,1-diethyl-n-oct-1-yl-,
1,1-diethyl-n-dec-1-yl-, 1,1-diethyl-n-dodec-1-yl-,
1,1-diethyl-n-tetradec-1-yl-, 1,1-diethyln-n-hexadec-1-yl-,
1,1-diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-,
1-(n-butyl)-cyclohex-1-yl-, 1-(n-hexyl)-cyclohex-1-yl-,
1-(n-octyl)-cyclohex-1-yl- and 1-(n-decyl)-cyclohex-1-yl. An
alkenyl group is understood to be ethenyl, propenyl, butenyl,
pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,
cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl, for
example. An alkynyl group is understood to be ethynyl, propynyl,
butynyl, pentynyl, hexynyl, heptynyl or octynyl, for example. A
C.sub.1 to C.sub.40 alkoxy group is understood to be methoxy,
trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
s-butoxy, t-butoxy or 2-methylbutoxy, for example.
One embodiment of the invention relates to organic molecules, which
have an .DELTA.E(S.sub.1-T.sub.1) value between the lowest excited
singlet (S.sub.1) state and the triplet (T.sub.1) state below it
that is no higher than 5000 cm.sup.-1, in particular no higher than
3000 cm.sup.-1, or no higher than 1500 cm.sup.-1 or 1000 cm.sup.-1
and/or an emission lifetime of at most 150 .mu.s, in particular at
most 100 .mu.s, at most 50 .mu.s, or at most 10 .mu.s and/or a main
emission band having a full width at half maximum (FWHM) of less
than 0.55 eV, in particular less than 0.50 eV, less than 0.48 eV,
or less than 0.45 eV.
The organic molecules according to the invention in particular have
an emission maximum between 430 and 520 nm, between 440 and 495 nm
or between 450 and 470 nm.
Due to the position of the emission maximum in the named region,
the organic molecules according to the invention are suitable for
use in displays, in particular in ultra-high definition displays,
in particular televisions (UHDTVs). The color space of a UHDTV is
determined according to the so-called Rec. 2020 Recommendation
(Recommendation ITU-R BT.2020) via the primary colors. For blue,
the optimum color point lies at a CIE.sub.x coordinate of 0.131 and
a CIE.sub.y coordinate of 0.046. At a full width at half maximum of
the blue emission band of 0 nm, this corresponds to an emission
maximum of 467 nm. As the full width at half maximum increases, the
optimum emission maximum for the blue primary color according to
Rec. 2020 occurs at shorter wavelengths, e.g. at 464 nm for a full
width at half maximum of 35 nm. Potential emission changes caused
by other components of the display are not taken into account for
this value. An ideal blue emitter for UHDTV applications therefore
has an emission maximum between 450 and 470 nm.
The molecules in particular have a "blue material index" (BMI), the
quotient of the PLQY (in %) and the CIE.sub.y color coordinate of
the light emitted by the molecule according to the invention, that
is greater than 120, in particular greater than 200, greater than
250 or greater than 300.
In a further aspect, the invention relates to a method for
producing an organic molecule according to the invention of the
type described here (with a possible subsequent reaction), wherein
a in 3 position R.sup.1-substituted and in 4 and 6 position
R.sup.2-substituted 2-bromo-5-fluorobenzonitrile is used as the
educt.
##STR00012##
In one embodiment, the corresponding coupling reactant is produced
by reacting in 3 position R.sup.1-substituted and in 4 and 6
position R.sup.2-substituted 2-bromo-5-fluorobenzonitrile with
bis(pinacolato)diboron
(4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi-1,3,2-dioxaborolane) in
situ, and converted in a palladium-catalyzed cross-coupling
reaction. The product is obtained by deprotonation of the
corresponding amine and subsequent nucleophilic substitution of the
fluorine groups. To do this, a nitrogen heterocyclic compound is
reacted with an educt Z1 in the context of a nucleophilic aromatic
substitution. Typical conditions include the use of a base, such as
potassium phosphate tribasic or sodium hydride, in an aprotic polar
solvent, such as dimethyl sulfoxide (DMSO) or N,N-dimethylformamide
(DMF).
In a further aspect, the invention relates to the use of the
organic molecules as luminescent emitters or as host material in an
organic optoelectronic device, in particular wherein the organic
optoelectronic device is selected from the group consisting of:
organic light-emitting diodes (OLEDs), light-emitting
electrochemical cells, OLED sensors, in particular in gas and vapor
sensors which are not hermetically shielded to the outside, organic
diodes, organic solar cells, organic transistors, organic
field-effect transistors, organic lasers and down-conversion
elements.
In a further aspect, the invention relates to a composition
comprising or consisting of:
(a) at least one organic molecule according to the invention, in
particular as an emitter and/or host, and
(b) at least one, i.e. one or more emitter and/or host materials,
that is or are different from the organic molecule according to the
invention, and
(c) optionally one or more dyes and/or one or more organic
solvents.
In one embodiment, the composition according to the invention
consists of an organic molecule according to the invention and one
or more host materials. In particular, the host material or
materials possess triplet (T.sub.1) and singlet (S.sub.1) energy
levels, which are energetically higher than the triplet (T.sub.1)
and singlet (S.sub.1) energy levels of the organic molecule
according to the invention. In one embodiment, in addition to the
organic molecule according to the invention, the composition has an
electron-dominant and a hole-dominant host material. The highest
occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) of
the hole-dominant host material are in particular energetically
higher than that of the electron-dominant host material. The HOMO
of the hole-dominant host material is energetically below the HOMO
of the organic molecule according to the invention, while the LUMO
of the electron-dominant host material is energetically above the
LUMO of the organic molecule according to the invention. In order
to avoid exciplex formation between emitter and host material or
host materials, the materials should be selected such that the
energy distances between the respective orbitals are small. The
distance between the LUMO of the electron-dominant host material
and the LUMO of the organic molecule according to the invention is
in particular less than 0.5 eV, preferably less than 0.3 eV, even
more preferably less than 0.2 eV. The distance between the HOMO of
the hole-dominant host material and the HOMO of the organic
molecule according to the invention is in particular less than 0.5
eV, preferably less than 0.3 eV, even more preferably less than 0.2
eV.
In a further aspect, the invention relates to an organic
optoelectronic device which comprises an organic molecule according
to the invention or a composition according to the invention.
The organic optoelectronic device is in particular formed as a
device selected from the group consisting of organic light-emitting
diode (OLED); light-emitting electrochemical cell; OLED sensor, in
particular gas and vapor sensors which are not hermetically
shielded to the outside; organic diode; organic solar cell; organic
transistor; organic field-effect transistor; organic laser and
down-conversion element.
An organic optoelectronic device comprising a substrate, an anode
and a cathode, wherein the anode or the cathode are disposed on the
substrate, and at least one light-emitting layer, which is disposed
between the anode and the cathode and which comprises an organic
molecule according to the invention, represents a further
embodiment of the invention.
In one embodiment, the optoelectronic device is an OLED. A typical
OLED, for example, has the following layer structure:
1. Substrate (supporting material)
2. Anode
3. Hole injection layer (HIL)
4. Hole transport layer (HTL)
5. Electron blocking layer (EBL)
6. Emitting layer (EML)
7. Hole blocking layer (HBL)
8. Electron transport layer (ETL)
9. Electron injection layer (EIL)
10. Cathode.
The presence of specific layers is merely optional. Several of
these layers can also coincide.
Specific layers can also be present more than once in the
component.
According to one embodiment, at least one electrode of the organic
component is designed to be translucent. In this case,
"translucent" describes a layer that is transmissive to visible
light. The translucent layer can be clearly translucent, i.e.
transparent, or at least partially light-absorbing and/or partially
light-diffusing, so that the translucent layer can, for example,
also be diffusely or milkily translucent. A layer referred to here
as translucent is in particular designed to be as transparent as
possible, so that in particular the absorption of light is as low
as possible.
According to a further embodiment, the organic component, in
particular an OLED, has an inverted structure. The inverted
structure is characterized in that the cathode is located on the
substrate and the other layers are disposed in a correspondingly
inverted manner:
1. Substrate (supporting material)
2. Cathode
3. Electron injection layer (EIL)
4. Electron transport layer (ETL)
5. Hole blocking layer (HBL)
6. Emission layer or emitting layer (EML)
7. Electron blocking layer (EBL)
8. Hole transport layer (HTL)
9. Hole injection layer (HIL)
10. Anode
The presence of specific layers is merely optional. Several of
these layers can also coincide. Specific layers can also be present
more than once in the component.
In one embodiment, in the inverted OLED, the anode layer of the
typical structure e.g. an ITO layer (indium tin oxide), is
connected as the cathode.
According to a further embodiment, the organic component, in
particular an OLED, has a stacked structure. In doing so, the
individual OLEDs are arranged one above the other and not next to
one another as usual. The production of mixed light can be made
possible with the aid of a stacked structure. This structure can be
used to produce white light, for example. To produce said white
light, the entire visible spectrum is typically imaged by combining
the emitted light of blue, green and red emitters. Furthermore,
with practically the same efficiency and identical luminance,
significantly longer lifetimes can be achieved in comparison to
conventional OLEDs. A so-called charge generation layer (CGL)
between two OLEDs is optionally used for the stacked structure.
Said layer consists of an n-doped and a p-doped layer, wherein the
n-doped layer is typically disposed closer to the anode.
In one embodiment--a so-called tandem OLED--two or more emission
layers occur between the anode and the cathode. In one embodiment,
three emission layers are arranged one above the other, wherein one
emission layer emits red light, one emission layer emits green
light and one emission layer emits blue light, and additional
charge generation, blocking or transport layers are optionally
disposed between the individual emission layers. In a further
embodiment, the respective emission layers are disposed directly
adjacent to one another. In another embodiment, one respective
charge generation layer is situated between the emission layers.
Emission layers that are directly adjacent to one another and
emission layers that are separated by charge generation layers can
furthermore be combined in an OLED.
An encapsulation arrangement can furthermore be disposed above the
electrodes and the organic layers as well. The encapsulation
arrangement can, for example, be designed in the form of a glass
cover or in the form of a thin-film encapsulation arrangement.
The supporting material of the optoelectronic device can, for
example, be glass, quartz, plastic, metal, a silicon wafer or any
other suitable solid or flexible, optionally transparent material.
The supporting material can, for example, comprise one or more
materials in the form of a layer, a film, a plate or a
laminate.
Transparent conductive metal oxides such as, for example, ITO
(indium tin oxide), zinc oxide, tin oxide, cadmium oxide, titanium
oxide, indium oxide or aluminum zinc oxide (AZO),
Zn.sub.2SnO.sub.4, CdSnO.sub.3, ZnSnO.sub.3, MgIn.sub.2O.sub.4,
GaInO.sub.3, Zn.sub.2In.sub.2O.sub.5 or In.sub.4Sn.sub.3O.sub.12 or
mixtures of different transparent conductive oxides, for example,
can be used as the anode of the optoelectronic device.
PEDOT:PSS (poly-3,4-ethylenedioxythiophene: polystyrene sulfonic
acid), PEDOT (poly-3,4-ethylenedioxythiophene), m-MTDATA
(4,4',4''-tris[phenyl(m-tolyl)amino]triphenylamine), Spiro-TAD
(2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9-spirobifluorene), DNTPD
(4,4'-bis[N-[4-{N,N-bis(3-methyl-phenyl)amino}phenyl]-N-phenylamino]biphe-
nyl), NPB
(N,N'-bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'--
diamine), NPNPB
(N,N'-diphenyl-N,N'-di-[4-(N,N-diphenyl-amino)phenyl]benzene),
MeO-TPD (N,N,N',N'-tetrakis(4-methoxyphenyl)benzene), HAT-CN
(1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile) or Spiro-NPD
(N,N'-diphenyl-N,N'-bis-(1-naphthyl)-9,9'-spirobifluorene-2,7-diamine),
for example, are suitable materials for an HIL. The layer thickness
is 10-80 nm, for example. Small molecules (e.g. copper
phthalocyanine (CuPc e.g. 10 nm thick)) or metal oxides, such as
MoO.sub.3, V.sub.2O.sub.5, can also be used.
Tertiary amines, carbazole derivatives, polyethylenedioxythiophene
doped with polystyrene sulfonic acid, polyaniline poly-TPD
(poly(4-butylphenyl-diphenyl-amine)) doped with camphorsulfonic
acid, [alpha]-NPD (poly(4-butylphenyl-diphenyl-amine)), TAPC
(4,4'-cyclohexylidene-bis[N,N-bis(4-methylphenyl)benzenamine]),
TCTA (tris(4-carbazoyl-9-ylphenyl)amine), 2-TNATA
(4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine), Spiro-TAD,
DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN or TrisPcz
(9,9'-diphenyl-6-(9-phenyl-9H-carbazole-3-yl)-9H,9'H-3,3'-bicarbazole)
can be used as materials for an HTL. The layer thickness is 10 nm
to 100 nm, for example.
The HTL can comprise a p-doped layer which has an inorganic or
organic dopant in an organic hole transporting matrix. Transition
metal oxides such as vanadium oxide, molybdenum oxide or tungsten
oxide, for example, can be used as the inorganic dopant.
Tetrafluorotetracyanoquinodimethane (F4-TCNQ), copper
pentafluorobenzoate (Cu(I)pFBz) or transition metal complexes can,
for example, be used as the organic dopants. The layer thickness is
10 nm to 100 nm, for example.
MCP (1,3-bis(carbazole-9-yl)benzene), TCTA, 2-TNATA, mCBP
(3,3-Di(9H-carbazole-9-yl)biphenyl), tris-Pcz
(9,9'-diphenyl-6-(9-phenyl-9H-carbazole-3-yl)-9H,9'H-3,3'-bicarbazole),
CzSi (9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole)
or DCB (N,N'-dicarbazolyl-1,4-dimethylbenzene) can, for example, be
used as the materials of an electron blocking layer. The layer
thickness is 10 nm to 50 nm, for example.
The emitter layer EML or emission layer consists of or contains
emitter material or a mixture comprising at least two emitter
materials and optionally one or more host materials. Suitable host
materials are, for example, mCP, TCTA, 2-TNATA, mCBP, CBP
(4,4'-bis-(N-carbazolyl)-biphenyl), Sif87
(dibenzo[b,d]thiophene-2-yltriphenylsilane), Sif88
(dibenzo[b,d]thiophene-2-yl)diphenylsilane) or DPEPO
(bis[2-((oxo)diphenylphosphino)phenyl]ether). The common matrix
materials, such as CBP, are suitable for emitter material emitting
in the green or in the red range or for a mixture comprising at
least two emitter materials. UHG matrix materials (ultra-high
energy gap materials) (see, for example, M. E. Thompson et al,
Chem. Mater. 2004, 16, 4743) or other so-called wide-gap matrix
materials can be used for emitter material emitting in the blue
range or a mixture comprising at least two emitter materials. The
layer thickness is 10 nm to 250 nm, for example.
The hole blocking layer HBL can, for example, comprise BCP
(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=bathocuproine),
bis-(2-methyl-8-hydroxyquinolinato)-(4-phenylphenolato)-aluminum(III)
(BAlq), Nbphen
(2,9-bis(naphthalene-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3
(aluminum-tris(8-hydroxyquinoline)), TSPO1
(diphenyl-4-triphenylsilyl-phenylphosphine oxide) or TCB/TCP
(1,3,5-tris(N-carbazolyl)benzene/1,3,5-tris(carbazole)-9-yl)benzene).
The layer thickness is 10 nm to 50 nm, for example.
The electron transport layer ETL can, for example, comprise
materials on the basis of AlQ.sub.3, TSPO1, BPyTP2
(2,7-di(2,2'-bipyridine-5-yl)triphenyl)), Sif87, Sif88, BmPyPhB
(1,3-bis[3,5-di(pyridine-3-yl)phenyl]benzene) or BTB
(4,4'-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1'-biphenyl). The
layer thickness is 10 nm to 200 nm, for example.
CsF, LiF, 8-hydroxyquinolinolatolithium (Liq), Li.sub.2O,
BaF.sub.2, MgO or NaF can be used as materials for a thin electron
injection layer EIL.
Metals or alloys, for example Al, Al>AlF, Ag, Pt, Au, Mg, Ag:Mg,
can be used as materials of the cathode layer. Typical layer
thicknesses are 100 nm to 200 nm. In particular, one or more metals
are used, which are stable when exposed to air and/or which are
self-passivating, for example by forming a thin protective oxide
layer.
Aluminum oxide, vanadium oxide, zinc oxide, zirconium oxide,
titanium oxide, hafnium oxide, lanthanum oxide, tantalum oxide, for
example, are suitable materials for encapsulation.
The person skilled in the art is well aware of which combinations
of materials can be used for an optoelectronic device containing an
organic molecule according to the invention.
In one embodiment of the organic optoelectronic device according to
the invention, the organic molecule according to the invention is
used as the emission material in a light-emitting layer EML,
wherein it is used either as a pure layer or in combination with
one or more host materials.
In another embodiment, the mass fraction of the organic molecule
according to the invention in the emitter layer EML of a
light-emitting layer in devices emitting optical light, in
particular in OLEDs, is between 1% and 80%. In one embodiment of
the organic optoelectronic device according to the invention, the
light-emitting layer is disposed on a substrate, wherein an anode
and a cathode are preferably disposed on the substrate and the
light-emitting layer is disposed between the anode and the
cathode.
The light-emitting layer can comprise only one organic molecule
according to the invention in 100% concentration, wherein the anode
and the cathode are disposed on the substrate, and the
light-emitting layer is disposed between the anode and the
cathode.
In one embodiment of the organic optoelectronic device according to
the invention, a hole- and electron-injecting layer is disposed
between the anode and the cathode, and a hole- and
electron-transporting layer is disposed between the hole- and
electron-injecting layer, and the light-emitting layer is disposed
between the hole- and electron-transporting layer.
In another embodiment of the invention, the organic optoelectronic
device has: a substrate, an anode, a cathode and at least one
respective hole- and electron-injecting layer, and at least one
respective hole- and electron-transporting layer, and at least one
light-emitting layer, the organic molecule according to the
invention and one or more host materials the triplet (T.sub.1) and
singlet (S.sub.1) energy levels of which are energetically higher
than the triplet (T.sub.1) and singlet (S.sub.1) energy levels of
the organic molecule, wherein the anode and the cathode are
disposed on the substrate, and the hole- and electron-injecting
layer is disposed between the anode and the cathode, and the hole-
and electron-transporting layer is disposed between the hole- and
electron-injecting layer, and the light-emitting layer is disposed
between the hole- and electron-transporting layer.
In a further aspect, the invention relates to a method for
producing an optoelectronic component. To do this, an organic
molecule according to the invention is used.
In one embodiment, the production method comprises the processing
of the organic molecule according to the invention by means of a
vacuum evaporation method or from a solution.
The invention also relates to a method for producing an
optoelectronic device according to the invention, in which at least
one layer of the optoelectronic device is coated using a
sublimation process, is coated using an OVPD (organic vapor phase
deposition) process, is coated using a carrier-gas sublimation,
and/or is produced from solution or using a pressure process.
Known methods are used for the production of the optoelectronic
device according to the invention. The layers are generally
disposed individually onto a suitable substrate in successive
deposition method steps. The common methods, such as thermal
evaporation, chemical vapor deposition (CVD), physical vapor
deposition (PVD) can be used for the vapor deposition. For active
matrix OLED (AMOLED) displays, deposition takes place onto an
AMOLED backplane as the substrate.
Layers can alternatively be deposited from solutions or dispersions
in suitable solvents. Spin coating, dip coating and jet pressure
methods are examples of suitable coating methods. According to the
invention, the individual layers can be produced via the same as
well as via respective different coating methods.
The invention will now be explained in more detail using the
following examples without the intent to thereby restrict said
invention.
EXAMPLES
General Synthesis Scheme
##STR00013## General Synthesis Specification AAV1:
##STR00014##
2-bromo-5-fluorobenzonitrile (2.00 equivalent),
bis(pinacolato)diboron (1.00 equivalent), pd.sub.2(dba).sub.3 (0.01
equivalent), SPhos (0.04 equivalent) and potassium phosphate
tribasic (6.00 equivalent) are stirred into a dioxane/water mixture
(ratio 20:1) at 110.degree. C. for 16 hours under nitrogen. The
insoluble constituents of the reaction mixture are subsequently
filtered off and washed with dioxane. The solvent of the filtrate
is removed and the obtained residue is dissolved in
dichloromethane, filtered through a small amount of silica gel, the
solvent is removed again and the thus obtained raw product is
purified by recrystallization from ethanol. The product is obtained
as a solid.
General Synthesis Specification AAV2:
##STR00015##
Z1 (1.00 equivalent), the corresponding donor molecule D-H (2.00
equivalent) and potassium phosphate tribasic (4.00 equivalent) are
suspended in DMSO under nitrogen and stirred at 110.degree. C. (16
h). The reaction mixture is then added to saturated sodium chloride
solution and extracted three times with dichloromethane. The
combined organic phases are washed twice with saturated sodium
chloride solution, dried over magnesium sulfate, and the solvent is
subsequently removed. Lastly, the raw product was purified by
recrystallization from toluene. The product is obtained as a
solid.
D-H in particular corresponds to a 3,6-substituted carbazole (e.g.
3,6-dimethylcarbazole, 3,6-diphenylcarbazole,
3,6-di-tert-butylcarbazole), a 2,7-substituted carbazole (e.g.
2,7-dimethylcarbazole, 2,7-diphenylcarbazole,
2,7-di-tert-butylcarbazole), an 1,8-substituted carbazole (e.g.
1,8-dimethylcarbazole, 1,8-diphenylcarbazole,
1,8-di-tert-butylcarbazole), a 1-substituted carbazole (e.g.
1-methylcarbazole, 1-phenylcarbazole, 1-tert-butylcarbazole), a
2-substituted carbazole (e.g. 2-methylcarbazole, 2-phenylcarbazole,
2-tert-butylcarbazole) or a 3-substituted carbazole (e.g.
3-methylcarbazole, 3-phenylcarbazole, 3-tert-butylcarbazole).
Photophysical Measurements
Pretreatment of Optical Glasses
All glasses (cuvettes and substrates made of quartz glass,
diameter: 1 cm) were cleaned after every use: washed three times in
each case with dichloromethane, acetone, ethanol, demineralized
water, placed in 5% Hellmanex solution for 24 h, thoroughly rinsed
with demineralized water. The optical glasses were dried by blowing
nitrogen over them.
Sample Preparation, Film: Spin Coating
Device: Spin150, SPS Euro.
The sample concentration was equivalent to 10 mg/ml, prepared in
toluene or chlorobenzene.
Program: 1) 3 s at 400 rpm; 2) 20 s at 1000 rpm at 1000 rpm/s. 3)
10 s at 4000 rpm at 1000 rpm/s. After coating, the films were dried
on a LHG precision heating plate for 1 min at 70.degree. C. in
air.
Photoluminescence Spectroscopy and TCSPC
Steady-state emission spectroscopy was carried out using a
fluorescence spectrometer of the company Horiba Scientific, Model
Fluoromax-4, equipped with a 150 W xenon arc lamp, excitation and
emission monochromators and a Hamamatsu R928 photomultiplier tube,
as well as a "Time-Correlated Single Photon Counting" (TCSPC)
option. The emission and excitation spectra were corrected by means
of standard correction curves.
The emission decay times were likewise measured on this system,
using the TCSPC method with the FM-2013 accessories and a TCSPC hub
of the company Horiba Yvon Jobin. Excitation sources:
NanoLED 370 (wavelength: 371 nm, pulse duration: 1.1 ns)
NanoLED 290 (wavelength: 294 nm, pulse duration: <1 ns)
SpectraLED 310 (wavelength: 314 nm)
SpectraLED 355 (wavelength: 355 nm).
The analysis (exponential fitting) was performed using the
DataStation software package and the DAS6 analysis software. The
fit was specified with the aid of the Chi-square method
.times..times. ##EQU00001## with e.sub.i: variable predicted by the
fit and o.sub.i: measured variable. Quantum Efficiency
Determination
The measurement of the photoluminescence quantum yield (PLQY) was
carried out by means of an Absolute PL Quantum Yield Measurement
C9920-03G system of the company Hamamatsu Photonics. Said system
consists of a 150 W xenon gas discharge lamp, automatically
adjustable Czerny-Turner monochromators (250-950 nm) and an
Ulbricht sphere with a high reflectance Spectralon coating (a
Teflon derivative), which is connected via a fiber optic cable to a
PMA-12 multichannel detector with a BT (back-thinned)-CCD chip
having 1024.times.122 pixels (size 24.times.24 .mu.m). The analysis
of the quantum efficiency and the CIE coordinates was carried out
using the software U6039-05 Version 3.6.0.
The emission maximum is measured in nm, the quantum yield Q is
measured in % and the CIE color coordinates are stated as x, y
values.
The photoluminescence quantum yield was determined according to the
following protocol:
1) Implementation of quality assurance measures: Anthracene in
ethanol at a known concentration serves as the reference
material.
2) Determination of the excitation wavelength: The absorption
maximum of the organic molecule was first determined and excited
with said wavelength.
3) Implementation of the sample measurement:
The absolute quantum yield of degassed solutions and films was
determined under a nitrogen atmosphere.
The calculation was performed within the system according to the
following equation:
.PHI..intg..lamda..function..function..lamda..function..lamda..times..tim-
es..times..lamda..intg..lamda..function..function..lamda..function..lamda.-
.times..times..times..lamda. ##EQU00002## with the photon number
n.sub.photon and the intensity Int.
Production and characterization of organic electroluminescence
devices from the gas phase With the organic molecules according to
the invention, OLED devices can be produced by means of vacuum
sublimation techniques.
These not yet optimized OLEDs can be characterized in the usual
manner. To do this, the electroluminescence spectra, the external
quantum efficiency (measured in %) as a function of the brightness
and calculated from the light detected by the photodiode, the
electroluminescence spectra and the current are recorded.
Example 1
##STR00016##
Example 1 was produced in accordance with AAV1 (Yield 29%) and AAV2
(Yield 13%).
Thin layer chromatography: R.sub.f=0.51 (cyclohexane/ethylacetate
5:1)
FIG. 1 shows the emission spectrum of Example 1 (10% in PMMA). The
emission maximum is at 448 nm. The photoluminescence quantum yield
(PLQY) is 82% and the full width at half maximum is 0.42 eV. The
CIE.sub.x color coordinate is 0.16 and the CIE.sub.y color
coordinate is 0.13.
Example 2
##STR00017##
Example 2 was produced in accordance with AAV1 (Yield 29%) and
AAV2.
Thin layer chromatography: R.sub.f=0,12 (cyclohexane/ethylacetate
5:1)
FIG. 2 shows the emission spectrum of Example 2 (10% in PMMA). The
emission maximum is at 491 nm. The photoluminescence quantum yield
(PLQY) is 77% and the full width at half maximum is 0.45 eV. The
CIE.sub.x color coordinate is 0.21 and the CIE.sub.y color
coordinate is 0.38.
Example 3
##STR00018##
Example 3 was produced in accordance with AAV1 (Yield 29%) and AAV2
Yield 83%).
Thin layer chromatography: R.sub.f=0.51 (cyclohexane/ethylacetate
5:1)
FIG. 3 shows the emission spectrum of Example 3 (10% in PMMA). The
emission maximum is at 520 nm. The photoluminescence quantum yield
(PLQY) is 62% and the full width at half maximum is 0.51 eV. The
CIE.sub.x color coordinate is 0.31 and the CIE.sub.y color
coordinate is 0.49.
Example 4
##STR00019##
Example 4 was produced according to AAV1 and AAV2.
Example 5
##STR00020##
Example 5 was produced in accordance with AAV1 (Yield 29%) and AAV2
(Yield 21%).
FIG. 4 shows the emission spectrum of Example 5 (10% in PMMA). The
emission maximum is at 444 nm. The photoluminescence quantum yield
(PLQY) is 91% and the full width at half maximum is 0.42 eV. The
CIE.sub.x color coordinate is 0.15 and the CIE.sub.y color
coordinate is 0.11.
Further examples of organic molecules having a structure according
to Formula I:
##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##
##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##
##STR00031## ##STR00032##
Although illustrative embodiments of the present invention have
been described herein with reference to the accompanying drawings,
it is to be understood that the invention is not limited to those
precise embodiments, and that various other changes and
modifications may be made by one skilled in the art without
departing from the scope or spirit of the invention.
* * * * *